Compositions containing discoloration inhibitors



' eans- 04 Patented Feb. 7, 1967 3,303,104 COMPGSETIONS CONTAININGDISCOLORATION INHIBITORS Fred K. Rubin, Bronx, N.Y., assignor to LeverBrothers Company, New York, N.Y., a corporation of Maine N Drawing.Filed Dec. 12, 1963, Ser. No. 329,958 18 Claims. (Cl. 252-99) Thisinvention relates to inhibitors suitable for retarding the discolorationof hard surfaces and more particularly, to synthetic detergentformulations suitable for dishwashing purposes and containingdiscoloration inhibitors.

Detergent compositions containing chlorinating compounds are now widelyused for many cleansing applications. It has been observed that metallicsurfaces such as gold, silver and platinum and non-metallic surfacesincluding chinaware, glass, porcelain and plastic surfaces such as arefound inside automatic dishwashing machines become discolored whencontacted with detergent formulations containing chlorinating agents inthe presence of manganese ion (Mn++) and particularly at elevatedtemperatures. Since the water of most communities contains manganese ionin concentrations high enough to cause discoloration of hard surfaces,it is apparent that a serious problem exists in this regard.

It is an object of this invention to prevent or diminish discolorationof hard surfaces caused by contact with halogenating agents in thepresence of manganese ion.

Another object is to prevent the discoloration of metallic andnon-metallic hard surfaces caused by contact with aqueous detergentcompositions containing halogenating agents in the presence of manganeseion.

Still another object of this invention is to prepare dishwashingcompositions suitable for washing dinner-ware decorated with a preciousmetal without discoloration of the metal.

An additional object is the preparation of compositions which may beadded to aqueous detergent solutions containing halogenating agents toinhibit the discoloration of hard surfaces which come in contact withthe detergent solution in the presence of manganese ion.

These and other objects and advantages are attained in accordance withthe present invention by providing compositions containing discolorationinhibitors selected from the group consisting of (1) compoundsfurnishing gluconate ion in aqueous solution and certain combinationsthereof with (2) cerium compounds or (3) certain inorganic persalts.These compositions prevent the discoloration of hard surfaces whichwould normally occur in the presence of halogenating agents andmanganese ion.

The materials which inhibit the discoloration of hard surfaces when thelatter are exposed to halogenating agents in aqueous solutionscontaining manganese ion are those which produce gluconate ion inaqueous solutions as well as compositions containing these compounds andother ingredients. The gluconate compounds which 'are employed in thisinvention are those materials which supply gluconate ion in aqueoussolution. Examples of gluconate salts which can be used are alkali metalgluconates such as sodium and potassium, ammonium gluconate, gluconicacid, alpha-sodium glucoheptonate dihydrate, glucono-delta-lacetone,etc.

Those compounds which furnish cerium ion in aqueous solutions can beutilized in combination with compounds furnishing gluconate ion toprevent or inhibit discoloration of hard surfaces. Any cerium compoundwhich fulfills the aforementioned requirement c'an be used. Examples ofthese compounds include cerium nitrate, cerium sulfate, cerium halidessuch as cerium chloride, etc.

It is preferred to use combinations of the gluconate and ceriuminhibitors rather than the gluconate alone. It has been found thatcombinations of these materials are particularly effective in preventingdiscoloration. As pointed out more particularly in the followingexamples, combinations of, for example, cerium nitrate and sodiumgluconate are considerably more effective as discoloration inhibitorsthan either of these compounds alone.

Furthermore, it has been discovered that combinations of gluconate saltssuch as sodium gluconate with watersoluble inorganic perborates anddipersulfates such as the alkali metal and ammonium salts thereof arealso efficacious in preventing or retarding the discoloration of hardsurfaces under the conditions described above. Examples of theseinorganic materials include sodium perborate and ammonium dipersulfate[(NH S O The proportions of discoloration inhibitor which can beemployed in this invention depend upon a number of variables and canbest be determined by those skilled in the ,art. Thus, the solubility ofthe inhibitor in aqueous solution is one factor and the level ofmanganese ion in the aqueous solution is still another factor indetermining the requisite proportion of inhibitor to be employed. Theamount of discoloration inhibitor which should be added to a compositionis the amount which is sufiicient to give the desired inhibition whenthe composition is used in its normal way such as for a dishwashingformulation.

It has been pointed out above that discoloration of hard surfaces occursin the presence of manganese ion and only when certain halogenatingcompounds are present. The following halogenating compounds have beenfound to induce discoloration: sodium and potassium.dichloroisocyanura-te, dichloroisocyanuric acid, trichloroisocyanuricacid, dichlorodimethylhydantoin, N,N- dichloro-p-toluene-sulfonamide,sodium chlorite and chlorine. These compounds cause discoloration whenused alone and when incorporated into detergent compositions. Elementalbromine has also been found to cause discoloration of hard surfaces. Theaforementioned materials have the following common characteristics: theyare all non-alkaline, inorganic and organic halogenating agents whichdiscolor hard surfaces in the presence of manganese ion. In the absenceof manganese ion or when these halogenating materials are removed from'the aqueous solution it is observed that no discoloration occurs.

Alkaline-reacting chlorinating compounds such as hypochlorites, e.g.,calcium and sodium hypochlorite, and chlorinated trisodium phosphate donot induce discoloration when added to aqueous solutions containingmanganese ion unless condensed inorganic polyphosphates such as sodiumtripolyphosphate are also present. These com densed polyphosphates donot discolor hard surfaces in the absence of halogenated agents eventhough manganese ion is present in the solution. Although highlyalkaline detergent formulations will not ordinarily cause discolorationeven when halogenating materials are present, this does not hold true ifthe compositions contain condensed phosphates. In the latter case, ithas been found necessary to add discoloration inhibitors.

The inhibitors of the invention can be admixed with the aforementionedhalogenating agents and this combination added to aqueous solutionscontaining manganese ion to prevent discoloration of hard surfacescoming in contact with the solutions. Alternatively, the inhibitors canbe utilized in various detergent formulations. Thus, the inhibitors areparticularly useful when added to conventional synthetic detergentcompositions of the type which contain one or more condensedpolyphosphates as builders and one or more synthetic anionic andnonionic detergents.

As another alternative the inhibitor either alone or in admixture withan inert filler such as sodium sulfate may be packaged separately andintroduced into the aqueous detergent solution prior to use thereof.Since local water conditions determine the extent of discoloration, thisembodiment offers a more practical solution to the problem.

Examples of detergents which may be present in formulations in which theinhibitors of the invention are compatible include alkyl arylsulfonates, alkyl aromatic sulfonic acids, esters of sulfuric acids withaliphatic alcohols of about -18 carbon atoms, sulfonated fatty oils,sulfated and sulfonated alkoxy derivatives and sulfuric acid esters ofmonoglycerides and glyceryl monoethers. The salts of these materials areordinarily employed.

The inhibitors are also useful with nonionic detergents such as forexample: alkylolamides of fatty acids, ethoxylated alcohols andthioalcohols, the nonionic detergents known as Pluronics which arepolyoxypropylene polymers containing varying amounts of ethylene oxidepresent as polyoxyethylene chains, etc.

The detergent compositions can also contain builders, fillers,soil-suspending agents and other conventional detergent ingredients. Thecompositions may also be prepared by conventional methods, such as byblending the ingredients in aqueous solution or slurry and thenspraydrying the mixture at elevated temperatures.

It is to be understood, however, that the invention is not concernedwith the preparation of detergent compositions and that the particulardetergent formulations to which the inhibitors of the invention can beadded are not critical. Some surfactants may be subject to attack by thehalogen-releasing agents when the compositions are stored. However,those skilled in the art can readily ascertain by sirnple trial whetherthe detergent and the halogenating agent are compatible.

In the following examples a test procedure has been de veloped tofacilitate the study of discoloration inhibitors. To acceleratediscoloration, the manganese ion concentration employed in these testsis considerably higher than the concentrations normally present in thewater used by the housewife. The concentrations of detergent andchlorinating agents correspond to those normally used in conventionalcommercial formulas.

In the test procedure the sample to be tested was weighed into a marked250 ml. Pyrex beaker, a platinum strip approximately mm. x 15 mm. x0.003 inch was suspended therein and about 200 ml. of water containingmanganese ion preheated to 145 F. was added. The beaker containing thetest solution and the platinum strip was then put into a water bathmaintained at a temperaure of about 143 F. After vigorous initialstirring to dissolve the sample, the test solution was agitated atfrequent intervals. Several samples and a control were testedsimultaneously and test solutions and platinum strips were observedclosely for discoloration and other changes. Fifteen minutes after theaddition of the water containing manganese ion, the platinum strips wereremoved from the solutions and examined. The strips were compared andgraded against a control and were reintroduced into the solutions for anadditional fifteen minute period. After a total exposure period of aboutthirty minutes, the platinum strips were again removed from the solutionand examined, compared and graded. In certain cases, this procedure wasvaried to extend the total exposure period of the strips to more thanthirty minutes.

Example I The following dishwashing formulation of a conventional typewas employed in the test described above:

Percent Sodium tripolyphosphate (containing some tetrapotassiumpyrophosphate) 45.0 Sodium metasilicate (1:1 ratio of Na O to SiO 26.0Dense soda ash 14.0 Sodium bicarbonate 6.5 Sodium alkyldiphenyloxidesulfonate active)- 0.6

- Exposure of Platinum Strip Percent Sodium Gluconate in solution 15mins. 30 mins.

None Heavy discoloration Heavy discoloration. 00125-00250 Noticeablereduction D0.

of discoloration. 0.0375 No discoloration Slight to moderately heavydiscoloration 0.050 do Very slight discoloration. 0.075 d0 Nodiscoloration.

The following table shows the results when lower levels of Mn are used:

Mn Sodium Concentra- Gluconate tion, p.p.m. Concentration, percentExposure of Pia-Strip 15 mins. 30 mins.

5 0. 050 No discoloratiom- Vetry slight discoloramm. 2.5 0. 025 Slighttrace of Slight discoloration.

discoloration. 1 0.010 No discoloration. Very slight to slightdiscoloration. 1 0.005 do Slight discoloration.

As a general guide to determining the requisite amount of gluconate tobe used, it has been found that about 05-30% sodium gluconate based onthe formula weight of the above composition was effective in retardingplatinum discoloration.

When the detergent active in the above formula was replaced by sodiumlauryl sulfate and lauryl hydroxyether sulfonate, the inhibiting effectof sodium gluconate remained unchanged.

Example I] Combinations of cerium nitrate and sodium gluconate wereconsiderably more effective as inhibitors than either of thesecomponents used alone. Thus, while 0.1% cerium nitrate was ineffectiveas an inhibitor and 5% sodium gluconate was only moderately effective, acombination of both agents at the stated concentrations pre venteddiscoloration completely during a l5-minute contact. The behavior ofcombinations of these ingredients under the test conditions described inExample I is set forth in the following table.

Plat. discoloration after contact Percent inhibitor period of- (basisdry formula wt.)

15 mins. 80 mins.

0.1 Ce(NO -6Hz0 Moderate/heavy--- Heavy. 0.2 Ce(NO -6H2O Do. 0.5 Oe(NO-6HzO Do. 1.0 Ce(N 6H2 Slight/moderate. 2.0 NO;) -6H2O Slight. 5.0Sodium Gluconate Heavy. 10.0 Sodium Gluconate Moderate/heavy. 15.0Sodium Gluconate N Slight. 20.0 Sodium Gluconate Practically none.

1 No appreciable increase in discoloration after 1.5 hr. contact period.1 Pronounced discoloration after 1.5 hr. contact period.

6 cedure described in Example I above. The results are tabulated below:

Discoloration after contact period of- Percent inhibitor in detergentsolution 15 mins. 30 mins. 60 mins.

None Heavy Heavy 0,0250 sodium gluconate Sli ht Moderate sogiumgluconate Moderate. Heavy 0 so ium g ucona e 0 0125 sodium perboratelNone N one (1) 0 0125 sodium gluconate (1) 0.0125 sodium perboratc 1Does not discolor even after 1 hr. of contact.

1 No appreciable increase in discoloration after 1.5 hr. contact period.2 Slight discoloration after 1.5 hr. contact period.

Generally, the combination of gluconate and cerium salt can be employedwithin the following range based on the results obtained with watercontaining 5 p.p.m. manganese ion: about 0.3% of cerium nitrate andsodium gluconate based on the total formula weight with the respectiveratios varying from about 1:2 to 1:50.

Example III It has been observed that cerium compounds are ineffectiveas platinum discoloration inhibitors in the absence of pyrophosphates.The data below shows that such is not the case when a combination of agluconate and a cerium compound is employed.

Chloritnating agent: 0.001375% potassium dichloroisocyanurate in aqueousso u ion. Mn++ concentration: 5 p.p.m.

Plat. discoloration after contact Percent inhibitor (basis dry formulawt.) period oimins. mins.

g g Heavy-m ye 3 3' 2 5.0 Sodium Gluconate Shght' 0.2 Ce(NO3);-6H2O doPractically 10.0 Sodium Gluconate none. 10.0 Sodium tripolyphosphate(TPP) contg. Hcavy Heavy.

approx. 10% sodium pyrophosphate. 10.0 TPP contg. approx. 10% sodiumpyrophosphate. None Practically 0.1 Ce(NO3)a-6H2O none. 5.0 SodiumGluconate 10.0 TPP contg. approx. 10% sodium pyrophosphate. do Do 0.2Ce(NOa)3-6H2O 10.0 Sodium Gluconate Example IV The behavior ofcombinations of gluconates with sodium perborate was tested inaccordance with the pro- A range of proportions of about 03-10% based onthe total formula weight for the combination of sodium perborate andsodium gluconate has been used with noticeable results. The respectiveratios of perborate to gluconate are about 1:2 to 1:10.

Example V It was discovered that combinations of dipersulfate salts andgluconates were only effective inhibitors when used with non-alkalinematerials such as chlorinating agents alone rather than admixed withdishwasher compositions containing alkaline builders. The proceduredescribed above for testing discoloration was varied in the case ofdipersulfates by employing a test solution containing only potassiumdichloroisocyanurate rather than a conventional detergent formulacontaining alkaline builders. The results of the tests were:

Platinum discoloration after contact period of- Percent inhibitor in0.0075% solution of potassium dichloroisoeyanurate 15 mins. 30 mins.

Heavy Heavy. Slight/moderate Moderate.

0.0025 sodium glucoinate. Moderate Heavy. 0.00 0 ammonium ipers 0.0065sodium gluconate None 0.00375 ammonium dipersu do D 0 0.01250 sodiumgluconate Example VI The use of inhibitors as additives to dishwashingsolutions or chlorinated sterilizing or rinse solutions in the form ofmixtures of inhibitor and inert diluent represents an important featureof the present invention. Typical combinations which have been preparedinclude the following:

Percent Sodium glueonate 25 Sodium sulfate 75 Ce(NO -6H O 0.2 Sodiumgluconate 10.0 Sodium sulfate 89.8

Sodium gluconate 4.0 Sodium perborate 4.0 Sodium sulfate 92.0

Ammonium dipersulfate 0.8 Sodium gluconate 2.5 Sodium sulfate 96.7

The above combinations when added to an automatic dishwasher at the samelevel as regular dishwasher detergents (i.e., to yield 0.25% solutions)prevent platinum discoloration in p.p.m. Mn++ water. Under practicalconditions less concentrated mixtures are feasible.

Composition D would be effective only in the absence of alkalinematerials. As explained above, dispersulfates do not inhibitdiscoloration when alkaline phosphates, silicates, soda ash, etc. arepresent. However, Composition D would be efiective in retardingdiscoloration in situations where non-alkaline chlorinating solutionwere employed to sterilize clean dishes or other surfaces which arenormally subject to discoloration under the conditions discussed above.

Example VII In another test a dishwasher product consisting of 8 ExampleVIII A. A sterling silver knife was exposed for 1 hr. in a 0.25%solution of a chlorinated dishwasher detergent of the type described inExample I above. The solution contained 5 p.p.m. Mn++ ion. Within 15minutes of exposure a yellow coating became noticeable on the knife;after 1 hour of exposure the coating had turned to a deepbrownish-orange. An identical knife, exposed for one hour to acorresponding dishwasher solution to which 0.065%

sodium gluconate had been added, did not discolor what- Example IX Thefollowing data illustrates the effectiveness of gluconates as inhibitorsof hypochlorite induced platinum discoloration. Calcium hypochlorite(Pittchlor, 70% available chlorine) and sodium hypochlorite (Clorox,5.3% available chlorine) were used in the example which was conducted inwater containing 5 p.p.m. Mn+ The water temperature was about 143 -F.

The calcium hypochlorite was incorporated in the following dishwasherdetergent:

Percent Sodium tripolyphosphate 45.0 Sodium metasilicate (Na O:SiO =1:1)26.0 Soda ash 14.0 Sodium bicarbonate 6.5 Sodium alkyldiphenyloxidesu-lfonate (85%) 0.6 Calcium hypochlorite (Pittehlor) 2.5

Sodium sulfate balance to 100.0.

This formula contains 1.75% available chlorine.

Platinum discoloration after exposure of 0.250% Calcium hypochloritedishwasher detergent. 0.050% Sodium gluconate.

Practically no discoloration.

}No discoloration B Percentage figures shown pertain to percentdetergent, inhibitor, etc. in the test solution.

98.9% of the detergent composition shown in Example I plus 1.0% sodiumgluconate+0.l% Ce(NO -6H O was employed to wash platinum trimmeddinnerware in an automatic dishwasher. After fifteen washes with thisformula, the platinum trimmings showed very slight discoloring.Identical dinnerware washed the same number of times with a controlcontaining no inhibitors discolored heavily after six washes. Theglassware spotting tendencies and lipstick removal properties of theformula containing the inhibitor were practically identical to those ofthe control.

Another product consisting of 99% of the composition shown in Example Iplus 1% sodium gluconate was emloyed to wash platinum trimmeddinnerware. After ten washes in the automatic dishwasher no discoloringoccurred. Moderate discoloring of the platinum trimmings becamenoticeable after twenty-one washes. A control caused severediscoloration after only six washes.

Similar results were obtained when sodium hypochlorite was added to asolution of the following nonchlorinated formula:

The addition of 0.45 ml. of sodium hypochlorite solution (Clorox) to oneliter of a 0.25% solution of the above nonchlorinated formula in watercontaining Mn++ yielded 23 p.p.m. available chlorine. This chlorinelevel is well within the available chlorine range of conventionaldishwasher detergent use solutions.

Platinum discoloration after exposure ofmins.

30 mtns.

0.250% Nonchlorinated formula.

0.045% Clorox 0.250% Nonchlorinated formula.

0.045% Clorox 0.050% Sodium gluconate-- Slight/moderate discoloration.

Severe discoloration.

Chlorine gas bub-bled through a solution containing Mn++ (to pH 3.5)also produced severe discoloration of platinum and the presence of 0.05%sodium gluconate vastly reduced the discoloration. Furthermore, thepresence of 0.05%0.075% sodium gluconate in a Mn++-containing solutionprevented the discoloration of platinum induced by 0.0375% DichloroamineT (58.5% av. Cl).

I claim:

1. A composition consisting essentially of a halogenating agent whichnormally discolors hard surfaces in the presence of manganese ions, saidhalogenating agent being selected from the group consisting ofchlorinating agents and elemental bromine, and a discolorationinhibiting amount of a material selected from the group consisting ofcompounds furnishing gluconate ion in aqueous solution, combinations ofcompounds furnishing said gluconate ion with compounds furnishing ceriumion in aqueous solution and combinations of compounds furnishing saidgluconate ion with a material selected from the group consisting ofammonium dipersulfate and sodium perborate, the composition being freeof alkaline materials when ammonium dipersulfate is employed.

2. The composition defined in claim 1 in combination with a syntheticnon-soap detergent.

3. The composition defined in claim 1 in combination with a condensedinorganic polyphosphate.

4. The composition defined in claim 1 in combination with a syntheticnon-soap detergent and a condensed inorganic .polyphosphate.

5. A composition according to claim 1 in which the gluconate ionfurnishing compound is selected from the group consisting of alkalimetal gluconates, ammonium gluconate, gluconic acid, alpha-sodiumglucoheptonate dihydrate and glucono delta-lactone.

6. A composition according to claim 1 in which the cerium compound isselected from the group consisting of cerium nitrate, cerium chlorideand cerium sulfate.

7. A composition according to claim 1 in which the inhibiting materialis a combination of a compound furnishing gluconate ions in aqueoussolution and a cerium compound.

8. A composition according to claim 1 in which the halogenating agent isa chlorine-containing agent selected from the grou consisting ofpotassium dichloroisocyanurate, sodium dichlorocyanurate,dichloroisocyanuric acid, trichloroisocyanuric acid,dichlorodimethylhydantoin, N, N-dichloro p-toluenesulfonamide, sodiumchlorite, chlorine, chlorinated trisodium phosphate and carcium andsodium hypochlorites.

9. A composition according to claim 1 in which the inhibitor is acombination of a compound furnishing gluconate ions in aqueous solutionand sodium perborate.

10. A composition according to claim 1 in which the inhibitor is acombination of a compound furnishing gluconate ions in aqueous solutionand ammonium dipersulfate.

11. A detergent formulation consisting essentially a condensed inorganicpolyphosphate, a synthetic non-soap detergent, an alkaline reactingchlorinating agent which normally discolors hard surfaces in thepresence of manganese ions and said polyphosphate, and a discolorationinhibiting amount of a compound selected from a group consisting ofcompounds furnishing 'gl-uconate ion in aqueous solution, combinationsof compounds furnishing said gluconate ion with compounds furnishingcerium ion in aqueuos solution and combinations of compounds furnishingsaid gluconate ion with sodium .perborate.

12. A detergent formulation according to claim 11 in which the syntheticdetergent is selected from the group consisting of anionic and nonionicsynthetic non-soap detergents.

13. A composition consisting essentially of at least one compound whichfurnishes gluconate ion in aqueous solution and at least one compoundwhich furnishes cerium ion in aqueous solution, said composition beingeffective in retarding the discoloring of hard surfaces when added tosolutions containing manganese ion and a halogenating agent whichnormally discolors hard surfaces in the presence of manganese ions, saidhalogenating agent being selected from the group consisting ofchlorinating agents and elemental bromine.

14. A composition consisting essentially of a combination of at leastone compound which furnishes gluconate ion in aqueous solution and atleast one watersoluble salt of a material selected from the groupconsisting of ammonium dipersulfate and sodium perborate, saidcombination being effective in retarding the discoloration of hardsurfaces when added to solutions containing manganese ion and ahalogenating agent which normally discolors hard surfaces in thepresence of manganese ions, said halogenating agent being selected fromthe group consisting of chlorinating agents and elemental bromine, thecompositions being free of alkaline materials when ammonium dipersulfateis employed.

15. A method of inhibiting the discoloration of hard surfaces resultingfrom exposure of the surface to a solution containing manganese ions anda halogenating agent which normally discolors hard surfaces in thepresence of manganese ions selected from the group consisting ofchlorinating agents and elemental bromine which comprises adding to thesolution a discoloration inhibiting amount of a material selected fromthe group consisting of compounds furnishing g-luconate ions in aqueoussolutions, combinations of compounds furnishing gluconate ions withcom-ponds furnishing cerium ions in aqueous solutions and combinationsof compounds furnishing gluconate ions 'with a material selected fromthe group consisting of ammonium dipersulfate and sodium perborate, saidsolution being free of alkaline materials when ammonium dipersulfate isemployed.

16. A method of inhibiting discoloration of a metallic surface resultingfrom exposure of the surface to a solution containing manganese ions anda halogeuating agent which normally discolors hard surfaces in thepresence of manganese ions selected from the group consisting ofchlorinating agents and elemental bromine which corn-prises adding tothe solution a discoloration inhibiting amount of a material selectedfrom the group consisting of compounds furnishing gluconate ions inaqueous solution, combinations of compounds furnishing gluconate ionswith compounds furnishing cerium ions in aqueous solution, andcombinations of compounds furnishing gluconate ions with a materialselected from the group consisting of ammonium dipersulfate and sodiumperborate, said solution being free of alkaline materials when ammoniumdipersulfate is employed.

17. A method of inhibiting the discoloration of nonmetallic hardsurfaces resulting from exposure of the surfaces to a solutioncontaining manganese ions and a halogenating agent which normallydiscolors hard surfaces in the presence of manganese ions selected fromthe group consisting of chlorinating agents and elemental bromine whichcomprises adding to the solution a discoloration inhibiting amount of amaterial selected from the group consisting of compounds furnishinggluconate ions in aqueous solution, combinations of compounds furnishingcerium ions in aqueous solution, and combinations of compoundsfurnishing gluconate ions with a material selected from the groupconsisting of ammonium dipersulfate and sodium perborate, said solutionbeing free of alkaline materials when ammonium dipersulfate is employed.

18. A composition effective in retarding the discoloration of hardsurfaces exposed to solutions containing manganese ions and halogenatingagents selected from the group consisting of chlorinating agents andelemental bromide which normally discolor hard surfaces in the presenceof manganese ions, said composition consisting essentially of an inertfiller and a compound selected from the group consisting of compoundsfurnishing gluconate ion in aqueous solution, combinations of saidgluconate with compounds furnishing cerium ion in aqueous ReferencesCited by the Examiner UNITED STATES PATENTS 2,689,225 9/1954 Anderson etal. 252-135 XR 3,049,495 8/1962 Jenkins et al. 252186 XR 3,112,27411/1963 Morgenthaler et al. 252-99 OTHER REFERENCES Gregory: Use andApplications of Chemicals and Related Materials, Reinhold Pub. Co.,N.Y., vol. 1 (1939), page 163 relied on.

Prescott et al.: Gluconic Acid and Its Derivatives, Ind. & Eng. Chem.,vol. 45, No. 2, February 1953, pp. 338-342.

LEON D. ROSDOL, Primary Examiner.

JULIUS GR EENWALD, Examiner.

M. WEINBLATT, Assistant Examiner.

UNITED STATES PATENT OFFICE Patent No. 3,303,104

February 7, 1967 Fred K, Rubin It is hereby certified that error appearsin the above numbered patent requiring correction and that the saidLetters Patent should read as corrected below.

Column 4, footnote 1, line 2 thereof, for "dischloroisocyanuric" readvdichloroisocyanuric column 9, line 59, for "carcium" read calcium line,68, after essentially" insert of column 11, line 9, after "furnishing"insert gluconate ions with compounds furnishing (SEAL) Attest:

Edward M. Fletcher, Jr.

Attesting Officer EDWARD J. BRENNER Commissioner of Patents

1. A COMPOSITION CONSISTING ESSENTIALLY OF A HALOGENATING AGENT WHICHNORMALLY DISCOLORS HARD SURFACES IN THE PRESENCE OF MANGANESE IONS, SAIDHALOGENATING AGENT BEING SELECTED FROM THE GROUP CONSISTING OFCHLORINATING AGENTS AND ELEMENTAL BROMINE, AND A DISCOLORATIONINHIBITING AMOUNT OF A MATERIAL SELECTED FROM THE GROUP CONSISTING OFCOMPOUNDS FURNISHING GLUCONATE ION IN AQUEOUS SOLUTION, COMBINATION OFCOMPOUNDS FURNISHING SAID GLUCONATE ION WITH COMPOUNDS FURNISHING CERIUMION IN AQUEOUS SOLUTION AN COMBINATIONS OF COMPOUNDS FURNISHING SAIDGLUCONATE ION WITH A MATERIAL SELECTED FROM THE GROUP CONSISTING OFAMMONIA DIPERSULFATE AND SODIUM PERBORATE, THE COMPOSITION BEING FREE OFALKALINE MATERIALS WHEN AMMONIUM DIPERSULFATE IS EMPLOYED.